Water-insoluble monoazo dyestuffs



United States Patent 3,438,967 WATER-INSOLUBLE MONOAZO DYESTUFFS Paul Rhyner, Base], and Klaus Artz, Muttenz, Switzerland, assignors to Ciba Limited, Basel, Switzerland, a Swiss company No Drawing. Filed Apr. 29, 1964, Ser. No. 363,616 Claims priority, application Switzerland, May 3, 1963, 5,585/63; Mar. 5, 1964, 2,847/64 Int. Cl. (30% 29/34; C07c 121/78; D06p 1/02 US. Cl. 260-2071 6 Claims The present invention provides new, valuable waterinsoluble monoazo dyestufi's of the formula in which A represents a benzene radical containing at most one nitro group, R represents a hydrogen atom or an alkyl or alkoxy group, R represents a cyanoalkoxyalkyl group, R represents a hydrogen atom or a cyanoalkoxyalkyl group or an acyloxyalkyl group, and X represents an acylamino group.

The new dyestuffs are obtained when a diazo compound of an aminobenzene containing at most one nitro group is coupled with a coupling component of the formula in which R R and R have the meanings given above. The amines to be used as diazo components advantageously contain a nitro group in para-position to the amino group, and advantageously correspond to the formula OgN NH:

in which Y represents a hydrogen or halogen atom or a cyanoor carbalkoxy group, and Z represents a hydrogen or halogen atom or an alkyl group.

The following amines may be mentioned as examples:

3,438,967 Patented Apr. 15, 1969 ice I-amino-2-trifluoromethyl-4-nitrobenzene, l-amino-2-chloro-4-nitrobenzene, 1-amino-2-cyano-4-nitrobenzene, and 1-amino-2-methylsulfonyl-4-nitrobenzene.

The coupling components used are advantageously amines of the formula a NHCORA in which R,, R and R have the meanings given above, and R represents a hydrogen atom or an alkyl, cycloalkyl or alkoxy group that may be substituted, and especially those of the formula R I 1 /CHzCHzOCH2CH2CN CHzCHzOCHzCHzCN NHCORA in which R, and R have the meanings given above.

Valuable results are likewise obtained with coupling components of the formulae NHCORA and in which R and R have the meanings given above, and alkyl may represent, for example, a methyl, ethyl or propyl group.

As examples the following coupling components may be mentioned:

NHCOCH:

Qwernomo crnoruoN):

NHCOC Z Qmomomo omornomg NHCHO CHzCHzO CHZCN N CHzCHzO C 0 CH NHCOCH:

Qnnomcmo onion NHCO CH2 Qnrtomomo cruoruoN NHCOC NHCOCHzCHa The above-mentioned coupling components may be obtained by known methods, for example, by additively combining 2 mols of acrylonitrile with the appropriate di-(hydroxyethyl)-aniline, or by additively combining 1 mol of acrylonitrile with the appropriate monohydroxyethylaniline, or by reacting a monocyanoethyl-di-(hydroxyethyl)-aniline with a carboxylic acid halide or anhydride.

The diazotization of the above-mentioned diazo components may be carried out by known methods, for example, with the aid of a mineral acid, especially hydrochloric acid, and sodium nitrite, or, for example, with a solution of nitrosyl-sulfuric acid in concentrated sulfuric acid.

The coupling may likewise be carried out by known methods, for example, in a neutral to acid medium, if desired or required, in the presence of sodium acetate or similar buffers or catalysts that influence the rate of coupling, for example, pyridine or salts thereof.

After the coupling reaction the dyestuffs formed may be separated from the coupling mixture, for example, by filtration because they are virtually insoluble in water.

Instead of the single diazo component, it is possible to use a mixture of two or more of the diazo components of the invention and, instead of a single coupling component, it is also possible to use a mixture of two or more of the coupling components of the invention.

After conversion into a finely divided form, the new monoazo dyestuffs are eminently suitable for the dyeing of synthetic fibers, especially fibers made of aromatic polyesters. They yield deep, orange to violet dyeings possessing a good fastness to light and to sublimation.

The following examples illustrate the invention. Unless otherwise stated, the parts and percentages are by weight.

EXAMPLE 1 C H2OH2O CHzCHzCN NHCOCH;

CH CHZO C OCH;

was precipitated by the addition of a saturated sodium acetate solution. The dyestuflf thus obtained dyed acetate silk, nylon, triacetate rayon and polyester fibers red tints.

4 EXAMPLE 2 17.25 parts of 1-amino-2-chloro-4-nitrobenzene were introduced in portions to 60 parts of concentrated sulfuric acid in which 6.9 parts of sodium nitrite had been dissolved. A clear, yellow solution was obtained by pouring the solution on to 400 parts of ice.

The diazo solution so obtained was added as in Example 1 to a solution of 33.3 parts of 3-acetamino-N- (fl-cyanoethoxyethyDN-acetoxyethylaniline in 200 ml. of 2 N hydrochloric acid. The dyestuff which was precipitated by the addition of sodium acetate dyed acetate silk, nylon, triacetate rayon and polyester fibers dark red tints.

EXAMPLE 3 16.3 parts of 1-amino-2-cyano-4-nitrobenzene were diazotized in the manner described in Example 2.

The diazo solution so obtained was added as in EX- ample 1 to a solution of 33.3 parts of 3-acetamino-N- (fi-cyanoethoxyethyl)-N-acetoxyethylaniline in 200 ml. of 2 N hydrochloric acid. The resulting dyestuff, which was completely precipitated by addition of sodium acetate, dyed acetate silk, nylon, triacetate rayon and polyester fibers violet tints.

EXAMPLE 4 19.6 parts of 1-amino-2-carbomethoxy-4-nitrobenzene were diazotized in the manner described in Example 2.

The diazo solution so obtained was added as in Example 1 to a solution of 33.3 parts of 3-acetamino-N-(fi-cyanoethoxyethyl)-N-acetoxyethylaniline in 200 ml. of 2 N hydrochloric acid. The dyestutf which was precipitated with sodium acetate dyed acetate silk, nylon, triacetate rayon and polyester fibers bluish red tints.

EXAMPLE 5 13.8 parts of l-amino-4-nitrobenzene were dissolved in 30 parts of water and 30 parts of concentrated hydrochloric acid. After the addition of parts of ice, 6.9 parts of ice, 6.9 parts of sodium nitrite were introduced and the mixture was stirred until the diazo solution was clear and almost colorless. The diazo solution so obtained was allowed to run into a solution that contained 0.1 mol of a mixture comprising 3-acetamino-N-(fi-cyanoethoxyethyl)-aniline and 3-acetamino-N:N-bis-(fl-cyanoethoxyethyl)-aniline in 200 ml. of 2 N. hydrochloric acid. By the addition of a saturated sodium acetate solution, a dyestuff was precipitated that dyed acetate silk, nylon, triacetate rayon and polyester fibers red tints possessing a very good fastness to light and sublimation.

The mixture of 3-acetamino-N-(fi-cyanoethoxyethyD- aniline and 3-acetamino N:N bis (B-cy'anoethoxyethyl)-aniline used as coupling component in this example could be obtained, for example, by heating 3- acetamino-amine with B cyanoethyl fi chlorethylether in the presence of an alkali. The ratio of monoand dialkylated product was determined by the reaction time.

After its titre had been determined, the crude product could be used directly for the manufacture of dyestuffs. The coupling components used in the following examples could be prepared by the same process.

EXAMPLE 6 17.25 parts of 1-amino-2-chloro-4-nitrobenzene were introduced in portions into 60 parts of concentrated sulfuric acid in which 6.9 parts of sodium nitrite had been dissolved. A clear, yellow solution was obtained by pouring the mixture on to 400 parts of ice.

The diazo solution so obtained was added as in Example 5 to 0.1 mol of a mixture comprising S-acetamino- N-(fi-cyanoethoxyethyl)-aniline and 3-acetamino N:N- bis-(fl-cyanoethoxyethyl)-aniline in 200 ml. of 2 N hydrochloric acid. The dyestuff precipitated by the addition of sodium acetate dyed acetate silk, nylon, triacetate rayon and polyester fibers red tints.

5 EXAMPLE 7 16.3 parts of 1-amino-2-cyano-4-nitrobenzene were diazotized in the manner described in Example 6.

The diazo solution so obtained was added as in EX- ample 5 to 0.1 mol of a mixture comprising 3-acetamino- N-(fl-cyanoethoxyethyl)-aniline and B-acetamino NzN- bis-(fi-cyanoethoxyethyl)-aniline in 200 ml. of 2 N hydrochloric acid and the dyestufi precipitated by the addition of sodium acetate. The dyestufi so obtained dyed acetate silk, nylon, triacetate rayon and polyester fibers violet tints.

EXAMPLE 8 19.6 parts of 1-amino-2-carbomethoxy-4-nitrobenzene were diazotized in the manner described in Example 2.

The diazo solution so obtained was added as in Example 5 to 0.1 mol of a mixture comprising 3-acetamino- N-(fi-cyanoethoxyethyl)-aniline and B-acetamino N:N-

6 bis-(fi-cyanoethoxyethyl)-aniline in 200ml. of 2 N hydrochloric acid. The dyestufl? precipitated by the addition of sodium acetate dyed acetate silk, nylon, triacetate rayon and polyester fibers red tints.

In the following table a number of further diazo com ponents are listed in Column 2 which when diazotizcd in the manner described in the preceding examples and coupled with a coupling component of the formula give similar dyestuffs. The meanings of R R R and X are indicated in Columns 3 to 6. The tints obtainable on polyester fibers with the said dyestuffs are indicated in Column 7.

N 0. DiflZO Compone t R1 a Ra X Tint on polyester fiber 28 Same as No. 27 above"..- H -C2H4O CQH-lCN H 'NHCOCH2CH3 Do.

29 OCH: H -C2H4OC2H4CN H -NHCOOC:H DO.

I NO

What is claimed is: 4. The dyestulf of the formula 1. Water-insoluble monoazo dyestuffs of the formula Y R1 OzNQN=N -N(CH C H 0 (3 momoml R2 C 01 1 1110 0 0 H2011;

R 5. The dyestufi. of the formula NHOOR; CH in which Y represents a member selected from the group 3 consisting of a hydrogen, a chlorine and bromine atom, ,C MOHZCHNCHZCNZCN a lower alkyl group, a lower alkoxy, a lower carbalkoxy and a cyano group, R represents a member selected 11310 OCH3 from the group consisting of a hydrogen atom, a lower alkyl and a lower salkoxy group, R represents a fl-cyano- The dyestufi of the formula ethoxyethyl group, R represents a member selected from the group consisting of a hydrogen atom, a B-cyano- C N(CH2OH20 CHZCHzCNh ethoxyethyl and a lower alkanoyloxyethyl group and R represents a member selected from the group consisting 0 CN NHCOCH: of lower alkyl and lower alkoxy groups. 3 R f C1 d 2. The dyestuff of the formula 6 erences l e FOREIGN PATENTS O2N- N=NQN(CH2CH2OCHzCHzCN): 204 5 1959 Austria NHCOCH3 36 CHARLES B. PARKER, Primary Examiner. The dyestufi the formula DONALD M. PAPUGA, Assistant Examiner. O N- 3-N=NQ-NHC mango CHZCHZCN Us. CL XR' NHCOCHa 

1. WATER-INSOLUBLE MONOAZO DYESTUFFS OF THE FORMULA 